Radical -Adenosyl-l-Methionine Enzyme PylB: A C-Centered Radical to Convert l-Lysine into (3)-3-Methyl-d-Ornithine.

PylB is a radical -adenosyl-l-methionine (SAM) enzyme predicted to convert l-lysine into (3)-3-methyl-d-ornithine, a precursor in the biosynthesis of the 22nd proteogenic amino acid pyrrolysine. This protein highly resembles that of the radical SAM tyrosine and tryptophan lyases, which activate their substrate by abstracting a H atom from the amino-nitrogen position. Here, combining assays, analytical methods, electron paramagnetic resonance spectroscopy, and theoretical methods, we demonstrated that instead, PylB activates its substrate by abstracting a H atom from the Cγ position of l-lysine to afford the radical-based β-scission.

Atomic-Layer Controlled Transition from Inverse Rashba-Edelstein Effect to Inverse Spin Hall Effect in 2D PtSe Probed by THz Spintronic Emission.

2D materials, such as transition metal dichalcogenides, are ideal platforms for spin-to-charge conversion (SCC) as they possess strong spin-orbit coupling (SOC), reduced dimensionality and crystal symmetries as well as tuneable band structure, compared to metallic structures. Moreover, SCC can be tuned with the number of layers, electric field, or strain. Here, SCC in epitaxially grown 2D PtSe by THz spintronic emission is studied since its 1T crystal symmetry and strong SOC favor SCC.

Intrinsic Flexibility beyond the Highly Ordered DNA Tetrahedron: An Integrative Spectroscopic and Molecular Dynamics Approach.

Since the introduction of DNA-based architectures, in the past decade, DNA tetrahedrons have aroused great interest. Applications of such nanostructures require structural control, especially in the perspective of their possible functionalities. In this work, an integrated approach for structural characterization of a tetrahedron structure is proposed with a focus on the fundamental biophysical aspects driving the assembly process.

Numerical Analysis of the Freezing Behavior of Saturated Cementitious Materials with Different Amounts of Chloride.

The freezing behavior of cement paste saturated with different chloride concentrations is investigated numerically with a coupled 3D hygro-thermo-mechanical FE analysis. The mathematical formulation of the freezing processes in the context of poromechanics takes into account the water (hydraulic) and ice pore pressures, as well as the distribution of heat (temperature) and strains. These quantities are calculated numerically based on three coupled differential equations, namely the static equilibrium equation and the equations for the transport of water and heat.

Catalytic Nitrene Transfer by an Fe -Imido Complex Generated by a Comproportionation Process.

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe and Fe precursors where the metal is embedded in a tetracarbene macrocycle.

A complete biomimetic iron-sulfur cubane redox series.

Synthetic iron-sulfur cubanes are models for biological cofactors, which are essential to delineate oxidation states in the more complex enzymatic systems. However, a complete series of [FeS] complexes spanning all redox states accessible by 1-electron transformations of the individual iron atoms ( = 0-4+) has never been prepared, deterring the methodical comparison of structure and spectroscopic signature. Here, we demonstrate that the use of a bulky arylthiolate ligand promoting the encapsulation of alkali-metal cations in the vicinity of the cubane enables the synthesis of such a series.

Electrocatalytic reduction of protons to dihydrogen by the cobalt tetraazamacrocyclic complex [Co(NH)Cl]: mechanism and benchmarking of performances.

The cobalt tetraazamacrocyclic [Co(NH)Cl] complex is becoming a popular and versatile catalyst for the electrocatalytic evolution of hydrogen, because of its stability and superior activity in aqueous conditions. We present here a benchmarking of its performances based on the thorough analysis of cyclic voltammograms recorded under various catalytic regimes in non-aqueous conditions allowing control of the proton concentration. This allowed a detailed mechanism to be proposed with quantitative determination of the rate-constants for the various protonation steps, as well as identification of the amine function of the tetraazamacrocyclic ligand to act as a proton relay during H evolution.

Independence of the Inverse Spin Hall Effect with the Magnetic Phase in Thin NiCu Films.

Large spin Hall angles have been observed in 3d ferromagnets, but their origin, and especially their link with the ferromagnetic order, remain unclear. Here, we investigate the evolution of the inverse spin Hall effect of Ni_{60}Cu_{40} and Ni_{50}Cu_{50} across their Curie temperatures using spin-pumping experiments. We show that the inverse spin Hall effect in these samples is comparable to that of platinum, and that it is insensitive to the magnetic order.

The valley Nernst effect in WSe.

The Hall effect can be extended by inducing a temperature gradient in lieu of electric field that is known as the Nernst (-Ettingshausen) effect. The recently discovered spin Nernst effect in heavy metals continues to enrich the picture of Nernst effect-related phenomena. However, the collection would not be complete without mentioning the valley degree of freedom benchmarked by the valley Hall effect.

Tuning the Electron Storage Potential of a Charge-Photoaccumulating Ru Complex by a DFT-Guided Approach.

Molecular photosensitizers that are able to store multiple reducing equivalents are of great interest in the field of solar fuel production, where most reactions involve multielectronic reduction processes. In order to increase the reducing power of a ruthenium tris-diimine charge-photoaccumulating complex, two structural modifications on its fused dipyridophenazine-pyridoquinolinone ligand were computationally investigated. Addition of an electron-donating oxime group was calculated to substantially decrease the reduction potentials of the complex, thus guiding the synthesis of a pyridoquinolinone-oxime derivative.

Radical S-Adenosyl-l-methionine Tryptophan Lyase (NosL): How the Protein Controls the Carboxyl Radical •CO Migration.

The radical S-adenosyl-l-methionine tryptophan lyase uses radical-based chemistry to convert l-tryptophan into 3-methyl-2-indolic acid, a fragment in the biosynthesis of the thiopeptide antibiotic nosiheptide. This complex reaction involves several successive steps corresponding to (i) the activation by a specific hydrogen-atom abstraction, (ii) an unprecedented •CO radical migration, (iii) a cyanide fragment release, and (iv) the termination of the radical-based reaction. In vitro study of this reaction is made more difficult because the enzyme produces a significant amount of a shunt product instead of the natural product.

An artificial photosynthetic system for photoaccumulation of two electrons on a fused dipyridophenazine (dppz)-pyridoquinolinone ligand.

Increasing the efficiency of molecular artificial photosynthetic systems is mandatory for the construction of functional devices for solar fuel production. Decoupling the light-induced charge separation steps from the catalytic process is a promising strategy, which can be achieved thanks to the introduction of suitable electron relay units performing charge accumulation. We report here on a novel ruthenium tris-diimine complex able to temporarily store two electrons on a fused dipyridophenazine-pyridoquinolinone π-extended ligand upon visible-light irradiation in the presence of a sacrificial electron donor.

Highly Efficient Spin-to-Charge Current Conversion in Strained HgTe Surface States Protected by a HgCdTe Layer.

We report the observation of spin-to-charge current conversion in strained mercury telluride at room temperature, using spin pumping experiments. We show that a HgCdTe barrier can be used to protect the HgTe from direct contact with the ferromagnet, leading to very high conversion rates, with inverse Edelstein lengths up to 2.0±0.

Evidence of Organic Luminescent Centers in Sol-Gel-Synthesized Yttrium Aluminum Borate Matrix Leading to Bright Visible Emission.

Yttrium aluminum borate (YAB) powders prepared by sol-gel process have been investigated to understand their photoluminescence (PL) mechanism. The amorphous YAB powders exhibit bright visible PL from blue emission for powders calcined at 450 °C to broad white PL for higher calcination temperature. Thanks to C labelling, NMR and EPR studies show that propionic acid initially used to solubilize the yttrium nitrate is decomposed into aromatic molecules confined within the inorganic matrix.

Spectroscopic evidence for cofactor-substrate interaction in the radical-SAM enzyme TYW1.

TYW1 is a metalloenzyme involved in the modifications of guanosine 37 of Phe-tRNA of Eukaryota and Archaea. It catalyzes the second step of Wybutosine biosynthesis, which consists of the formation of the tricyclic compound imG-14 from mG using pyruvate and SAM (S-adenosyl-methionine) as co-substrates. Two [4Fe-4S] clusters are needed in the catalytic process.

Ligand and Metal Based Multielectron Redox Chemistry of Cobalt Supported by Tetradentate Schiff Bases.

We have investigated the influence of bound cations on the reduction of cobalt complexes of redox active ligands and explored the reactivity of reduced species with CO. The one electron reduction of [Co(salophen)] with alkali metals (M = Li, Na, K) leads to either ligand-centered or metal-centered reduction depending on the alkali ion. It affords either the [Co(salophen)K] complexes or the [Co(bis-salophen)M] (M = Li, Na) dimers that are present in solution in equilibrium with the respective [Co(salophen)M] complexes.

Evidence for spin-to-charge conversion by Rashba coupling in metallic states at the Fe/Ge(111) interface.

The spin-orbit coupling relating the electron spin and momentum allows for spin generation, detection and manipulation. It thus fulfils the three basic functions of the spin field-effect transistor. However, the spin Hall effect in bulk germanium is too weak to produce spin currents, whereas large Rashba effect at Ge(111) surfaces covered with heavy metals could generate spin-polarized currents.

Redox Behavior of the S-Adenosylmethionine (SAM)-Binding Fe-S Cluster in Methylthiotransferase RimO, toward Understanding Dual SAM Activity.

RimO, a radical-S-adenosylmethionine (SAM) enzyme, catalyzes the specific C methylthiolation of the D89 residue in the ribosomal S protein. Two intact iron-sulfur clusters and two SAM cofactors both are required for catalysis. By using electron paramagnetic resonance, Mössbauer spectroscopies, and site-directed mutagenesis, we show how two SAM molecules sequentially bind to the unique iron site of the radical-SAM cluster for two distinct chemical reactions in RimO.

Unanticipated coordination of tris buffer to the Radical SAM cluster of the RimO methylthiotransferase.

Radical SAM enzymes generally contain a [4Fe-4S](2+/1+) (RS cluster) cluster bound to the protein via the three cysteines of a canonical motif CxxxCxxC. The non-cysteinyl iron is used to coordinate SAM via its amino-carboxylate moiety. The coordination-induced proximity between the cluster acting as an electron donor and the adenosyl-sulfonium bond of SAM allows for the homolytic cleavage of the latter leading to the formation of the reactive 5'-deoxyadenosyl radical used for substrate activation.

Spin to Charge Conversion at Room Temperature by Spin Pumping into a New Type of Topological Insulator: α-Sn Films.

We present results on spin to charge current conversion in experiments of resonant spin pumping into the Dirac cone with helical spin polarization of the elemental topological insulator (TI) α-Sn. By angle-resolved photoelectron spectroscopy (ARPES), we first check that the Dirac cone (DC) at the α-Sn (0 0 1) surface subsists after covering Sn with Ag. Then we show that resonant spin pumping at room temperature from Fe through Ag into α-Sn layers induces a lateral charge current that can be ascribed to the inverse Edelstein effect by the DC states.

Spin transport in p-type germanium.

We report on the spin transport properties in p-doped germanium (Ge-p) using low temperature magnetoresistance measurements, electrical spin injection from a ferromagnetic metal and the spin pumping-inverse spin Hall effect method. Electrical spin injection is carried out using three-terminal measurements and the Hanle effect. In the 2-20 K temperature range, weak antilocalization and the Hanle effect provide the same spin lifetime in the germanium valence band (≈1 ps) in agreement with predicted values and previous optical measurements.

Enhanced Spin Pumping Efficiency in Antiferromagnetic IrMn Thin Films around the Magnetic Phase Transition.

We report the measurement of a spin pumping effect due to fluctuations of the magnetic order of IrMn thin films. A precessing NiFe ferromagnet injected spins into IrMn spin sinks, and enhanced damping was observed around the IrMn magnetic phase transition. Our data were compared to a recently developed theory and converted into interfacial spin mixing conductance enhancements.

-Heptazine oligomers: promising structural models for graphitic carbon nitride.

Graphitic carbon nitride (g-CN) has interesting catalytic properties but is difficult to study due to its structure and how it is produced. In this study, linear -heptazine oligomers were synthesized to serve as well-defined molecular models for g-CN. Cyclic voltammetry, absorption and emission spectroscopies showed a clear shift of properties towards those of g-CN as the number of heptazine units increased.